Polyurethaneurea system

ABSTRACT

A polyurethaneurea system that includes in some embodiments Parts A and B reaction components for a polyurethaneurea, wherein an exemplary embodiment provides a Part A that comprises between 55 and 75 wt. % of an oligomeric polyol, between 3 and 7 wt. % of an aromatic diamine chain extender, and between 0.1 and 1.5% of a reactivity catalyst; Part B includes between 1 and 15 wt. % of a short aromatic diisocyanate and between 5 and 35 wt. % of an aromatic diisocyanate prepolymer that is the reaction product of a short aromatic diisocyanate and a diol. The polyurethaneurea system may further comprise an elastomer-surface activator comprising a second short aromatic diisocyanate and a second aromatic diisocyanate prepolymer, wherein at least one of the second diisocyanates may be the same as at least one of the diisocyanates of Part B.

This application is a continuation-in-part of International ApplicationNo. PCT/US07/83019 filed Oct. 30, 2007, which was a continuation-in-partof International Application No. PCT/US06/42138 filed Oct. 30, 2006.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to polyurethaneurea systems and moreparticularly, to polyurethaneurea systems useful for bonding and fillingelastomers, especially elastomers comprising cross-linked rubber.

2. Description of the Related Art

Various adhesive products, including polyurethane adhesive products, arecommercially available to use as sealants or to patch polymericelastomeric materials such as, for example, natural rubber, syntheticrubber, plasticized polyvinyl chloride, polychloroprene and the like.

Polyurethanes are typically synthesized from a polyisocyanate, apolyglycols and a chain extender. The chain extender is typicallyselected from a low molecular weight diol, diamine, aminoalcohol orwater. When the chain extender is a diol, the polyurethane that isformed consists entirely of urethane linkages. However, if, for example,the chain extender is water, aminoalcohol or a diamine, both urethaneand urea linkages are present and the resulting composition is called apolyurethaneurea or PUU. Therefore, a polyurethane type compositionhaving both urethane and urea linkages may be called a polyurethaneurea.

SUMMARY OF THE INVENTION

Particular embodiments of the present invention include apolyurethaneurea system that is useful for bonding and/or repairing anelastomer. The system includes reaction components that react to form apolyurethaneurea, the reaction components including a Part A and a PartB. These Parts may comprise mixtures as follows, with the mass fractionof each of the reaction components based upon the total mass of the partA and part B reaction components: Part A is a mixture comprising betweenabout 55 and about 75 wt. % of an oligomeric polyol (a primary polyol insome embodiments) having an average molecular weight greater than about1000, between about 3 and about 7 wt. % of an aromatic diamine chainextender, and between about 0.1 and about 1.5% of a reactivity catalyst;Part B is a mixture comprising between about 1 and about 15 wt. % of ashort aromatic diisocyanate and between about 5 and about 35 wt. % of anaromatic diisocyanate prepolymer that is the reaction product of a shortaromatic diisocyanate and a diol. Particular embodiments of thepolyurethaneurea system provide that a ratio of isocyanatefunctionalities to a total of the amine and hydroxyl functionalities inthe mixture of part A and part B is between about 0.8 and about 2.Alternatively, particular embodiments provide that the ratio is betweenabout 1 and about 1.07.

The polyurethaneurea system may further comprise an elastomer-surfaceactivator comprising a second short aromatic diisocyanate and a secondaromatic diisocyanate prepolymer, wherein at least one of the seconddiisocyanates may be the same as at least one of the diisocyanates ofPart B.

Particular embodiments of the present invention further provide aprocess, comprising reacting the reaction components of thepolyurethaneurea system described above. The method may further includeapplying the polyurethaneurea to a face of a cross-linked rubber articleand bonding the face of the cross-linked rubber article to a substrate.Particular embodiments of the process may further include applying anelastomer-surface activator to the face of the cross-linked rubberarticle, wherein the elastomer-surface activator comprises a secondshort aromatic diisocyanate and a second aromatic diisocyanateprepolymer. Optionally, the process may include priming the face of thecross-linked rubber article with a solution of trichloroisocyanuric acidin a solvent.

Particular embodiments of the present invention further include articlescomprising a component bonded to the article with the polyurethaneureasystem described above.

Particular embodiments of the present invention provide a method forretreading a tire, including applying the elastomer-surface activator toa bonding surface of a tread band, applying the polyurethaneureamaterial to the bonding surface of the tread band, and placing thebonding surface of the tread band having the polyurethaneurea materialthereon onto an outer bonding surface of a tire carcass.

Particular embodiments of the present invention further provide a methodof repairing an elastomeric article, comprising coating a damagedsurface of the elastomeric article with the elastomer-surface activator,wherein the damaged surface is an exposed surface of a hole, gash,gouge, split, cut or tear in the article; and filling the hole, gash,gouge, split, cut or tear in the article with the polyurethaneureadescribed above.

The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescription of a preferred embodiment of the invention, as illustratedin the accompanying drawing wherein like reference numbers representlike parts of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph plotting elongation and modulus of different rubbercompositions and an exemplary polyurethaneurea material in accordancewith the present invention.

FIG. 2 is a graph plotting strain and true stress of different rubbercompositions and an exemplary polyurethaneurea material in accordancewith the present invention.

FIG. 3 is a graph plotting elongation and hysteresis of different rubbercompositions and an exemplary polyurethaneurea material in accordancewith the present invention.

FIG. 4 is a graph plotting break stress and break strain of severaldifferent rubber compositions bonded with exemplary polyurethaneureasystems in accordance with the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention includes a polyurethaneurea system, methods of itsmaking and methods of its use. The polyurethaneurea system is useful asan adhesive and/or as a repair material for various articles, includingelastomeric articles and including elastomeric articles that comprise across-linked (cured) rubber compound. The polyurethaneurea system isuseful as a repair material to fill holes, gashes, gouges, splits, cuts,tears and/or other damage resulting in a loss of the original material,including elastomeric material, that is to be repaired. The presentinvention further includes articles having the polyurethaneurea as anadhesive and/or repair material. In particular embodiments, thepolyurethaneurea is useful for securing a patch to an elastomer article.The polyurethaneurea system is useful for repairing elastomer articlesincluding elastomeric articles that comprise a cross-linked (cured)rubber compound without requiring the repair to be cured at a hightemperature.

The polyurethaneurea system of particular embodiments provides apolyurethaneurea product resulting from the reaction of Part A and PartB reaction components. Part A may comprise a mixture of reactioncomponents including an oligomeric polyol and an aromatic diamine chainextender while Part B may comprise a mixture of reaction componentsincluding a short aromatic diisocyanate and an aromatic diisocyanateprepolymer, the prepolymer being the reaction product of a shortaromatic diisocyanate with a diol. Advantageously, particularembodiments include no solvent and/or no fillers in the Part A and PartB mixtures.

The mixture of the Part A and Part B reaction components may becharacterized in some embodiments as having a ratio of isocyanatefunctionalities to a total of the amine and hydroxyl functionalities inthe mixture of between about 0.9 and about 2. Other embodiments havesuch a ratio of between about 1 and about 1.7 while other embodimentshave a ratio of between about 1 and about 1.07 or between about 1 andabout 1.03.

The Part A mixture used to form the polyurethaneurea system ofparticular embodiments includes an oligomeric polyol and an aromaticdiamine chain extender. The oligomeric polyol reacts to form theurethane linkages in the polyurethaneurea composition. Particularembodiments include an oligomeric polyol having an average molecularweight greater than about 1000 or between about 1000 and 4000 whileother embodiments include a polyol having an average molecular weight ofbetween about 1500 and 4000 or between about 2000 and about 4000. Allmolecular weights are expressed throughout as weight average molecularweights unless otherwise indicated.

The oligomeric polyol reaction component of particular embodiments maybe characterized as having no oligomeric polyol having a molecularweight of less than about 1000 or alternatively, less than about 900 orless than about 800. Alternatively, in particular embodiments, theoligomeric polyol may include no more than about 5 wt. % oralternatively no more than about 10 wt. %, 15 wt. % or about 25 wt. % ofoligomeric polyol having a molecular weight of less than about 1000,less than about 900 or less than about 800 respectively.

The oligomeric polyol reaction component of particular embodiments mayfurther be characterized as being predominately a primary oligomericpolyol. For example, some embodiments may include an oligomeric polyolas being 100 wt. % primary oligomeric polyol or alternatively at least95 wt. % primary oligomeric polyol or at least 75 wt. % primaryoligomeric polyol. Particular embodiments include an oligomeric polyolreaction component having an OH functionality of about 2.

Non-limiting examples of suitable primary oligomeric polyols includepolyether polyols, amine-terminated polyols, polyester polyols,polyester ether polyols, polycyclic polyols and polycarbonate polyols.Polyether polyols include polytetramethylene ether glycol (PTMEG).Amine-terminated polyols are based on polyether glycols that have hadthe terminal hydroxyl groups replaced by primary or secondary aminofunctionalities. The polyester polyol may include, for example,polyethylene adipates, polyethyleneglycol adipates, polycaprolactonediols, and polycaprolactone-polyadipate copolymer diols.

For those embodiments that do not include only a primary oligomericpolyol, then secondary polyols, for example, may be included in as areaction component in particular embodiments. Such secondary oligomericpolyol may include, for example, polybutylene oxide glycol (PBO),polypropylene oxide glycol (PPO) and castor oil.

Optionally, the oligomeric polyol reaction component may includemixtures of oligomeric polyol selected from those described above and/orfrom others as known to those having ordinary skill in the art.

Particular embodiments include an amount of the oligomeric polyolreaction component (expressed as the wt. % of the total mass of thereactant components of Part A and Part B) as being between about 50 wt.% and about 80 wt. % of the total mass or alternatively between about 55wt. % and about 75 wt. % or between about 60 wt. % and about 72 wt. %.

Another reaction component that may be included in the Part A mixture isan aromatic diamine chain extender. The aromatic diamine chain extenderreacts to form the urea linkages in the polyurethaneurea reactionproduct. The aromatic diamine chain extender may be, for example, aprimary and/or a secondary aromatic diamine. Particular embodimentsinclude only primary aromatic diamine or the aromatic diamine reactioncomponent may include, for example, at least 75 wt. % or at least 95 wt.% primary aromatic diamine.

Non-limiting examples of the aromatic diamine chain extender reactioncomponent include 2,4 and 2,6 isomers of DETDA (diethyltoluenediamine),methylenebis(N,N-dibutyldianiline), IPDA (isophoronediamine), or3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamineisomers or mixtures thereof. Other examples include methylene dianiline(MDA), 4,4′-methylene-bis-3-(chloro-2,6-diethylbenzenamine) (MCDEA);4,4′-methylene-bis-(2-ethyl-6-methylaniline) (MMEA);4,4′-bis-(2,6-diethylaniline) (MDEA);4,4′-methylene-bis-(2-isopropyl-6-methylaniline) (MMIPA);4,4′-bis(sec-butylamino)diphenylmethane; phenyl-enediamine;methylene-bis-orthochloroaniline (MBOCA);4,4′-methylene-bis-(2-methyl-aniline) (MMA);4,4′-methylene-bis-(2-chloro-6-ethylaniline) (MCEA);1,2-bis(2-amino-phenylthio)ethane; N,N′-di-alkyl-p-phenylenediamine;4,4′-methylene-bis(2,6-diisopropylaniline) (MDIPA);dimethylthiotol-uenediamine (DMTDA) or mixtures thereof.

Optionally, the aromatic diamine chain extender reaction component mayinclude mixtures of aromatic diamine chain extender selected from thosedescribed above and/or from others as known to those having ordinaryskill in the art.

Particular embodiments include an amount of the aromatic diamine chainextender reaction component (expressed as the wt. % of the total mass ofthe reactant components of Part A and Part B) as being between about 0wt. % and about 10 wt. % of the total mass or alternatively betweenabout 5 wt. % and about 7 wt. % or between about 3.5 wt. % and about 5wt. %.

The Part B mixture used to form the polyurethaneurea system ofparticular embodiments includes a short aromatic diisocyanate and aprepolymer. The prepolymer may be formed of a short aromaticdiisocyanate and a diol. A short aromatic diisocyanate is typically anon-polymerized component.

The short aromatic diisocyanate reaction component included inparticular embodiments may be characterized as being a low-viscosityliquid at room temperature for ease of handling; e.g., a short aromaticdiisocyanate having a viscosity of between about 20 and about 30 cps at25° C. The short aromatic diisocyanate reaction component typically hasa molecular weight that is less than about 500 with particularembodiments having a molecular weight of between 160 and 500 oralternatively between 160 and 300. In particular embodiments, the shortaromatic diisocyanate reaction component may have a isocyanatefunctionality of 2 or alternatively, between about 1.8 and 2.2 orbetween about 1.9 and about 2.1.

Non-limiting examples of suitable short aromatic diisocyanates include,for example, phenylene diisocyanate, p- and m-phenylene diisocyanates;toluene diisocyanates, xylene diisocyanates, 2, 4 and/or 2,6 toluenediisocyanates (TDI), 1,5-naphthalene diisocyanate; carbodimide modifiedmethylene diisocyanate, 4,4′-diphenyl-methane diisocyanate (MDI) and, ifappropriate, its higher homologues (polymeric MDI), modified MDIcompounds, naphthalene diisocyanates (NDI), isomer mixtures ofindividual aromatic diisocyanates or combinations thereof. An example ofa modified MDI compound that is useful as a short aromatic diisocyanateis a polycarbodiimide-modified diphenylmethane diisocyanate such as isavailable from the Dow Chemical Company as ISONATE 143L.

Particular embodiments include an amount of the short aromaticdiisocyanates reaction component (expressed as the wt. % of the totalmass of the reactant components of Part A and Part B) as being betweenabout 0 wt. % and about 25 wt. % of the total mass or alternativelybetween about 1 wt. % and about 15 wt. % or between about 1 wt. % andabout 13 wt. %.

The aromatic diisocyanate prepolymer reaction component of the Part Bmixture of the polyurethaneurea system may in particular embodiments becharacterized as the reaction product between a short aromaticdiisocyanate as described above and a diol. The aromatic diisocyanateprepolymer may further be characterized as having an isocyanatefunctionality of 2 or alternatively, between about 1.8 and 2.2 orbetween about 1.9 and about 2.1.

In particular embodiments, the diol reacted to form the aromaticdiisocyanate prepolymer is a primary diol. In particular embodiments,the diol used to form the prepolymer may be 100 wt. % a primary diol,may be greater than about 95 wt. % a primary diol, may be greater thanabout 75 wt. % a primary diol or may be greater than about 50 wt. % aprimary diol. Particular embodiments include a diol having a molecularweight of between about 250 and about 3000 or alternatively, betweenabout 400 and about 2000.

Typically, suitable prepolymers may have a molecular weight that isgreater than 500 or that is between about 500 and about 4000. Otherembodiments include prepolymers having a molecular weight that isbetween about 800 and about 3000 or alternatively, between about 850 andabout 1500.

A useful prepolymer as a reaction component for particular embodimentsmay be the reaction product of a short aromatic diisocyanate and apolyether or polyester-based primary diol. An example of a usefulpolyether-based aromatic diisocyanate prepolymer is a polyether-baseddiphenylmethane diisocyanate terminated prepolymer such as is availablefrom Chemtura as VIBRATHANE B836. This prepolymer is the reactionproduct of a polyether with diphenylmethane diisocyanate (MDI).

Particular embodiments include an amount of the aromatic diisocyanateprepolymer reaction component (expressed as the wt. % of the total massof the reactant components of Part A and Part B) as being between about0 wt. % and about 50 wt. % of the total mass or alternatively betweenabout 5 wt. % and about 45 wt. % or between about 10 wt. % and about 35wt. %.

The pot life, or the time limit for use of the polyurethaneureaadhesive/repair material before it becomes too viscous to spread, may bebetween about 1.5 and about 4 minutes at 40° C. after the reactioncomponents (Part A and Part B) have been mixed together. Particularembodiments of the polyurethaneurea system may therefore include, as areaction component, a reactivity catalyst that is useful to adjust thepot life, as known to those having ordinary skill in the art. Anexemplary reactivity catalyst is alicyclic (cyclo-aliphatic) tertiaryamine such as triethylenediamine.

The reactivity catalyst may be typically added to the reactioncomponents at between about 0.1 and about 1.5 wt. % of the totalreaction components (Part A and Part B). In other embodiments, thereactivity catalyst may be added to the reaction components at betweenabout 0 and about 15 wt. %, between about 0.05 and about 9 wt. % orbetween about 0.4 and about 1 wt. %.

It was found that in particular embodiments, the omission of thecatalyst provided a polyurethaneurea material that was much more rigidand quite opaque when compared to the material of other embodiments thatresulted when the catalyst was added. Particular embodiments thatinclude the reactivity catalyst advantageously provide apolyurethaneurea material that is typically similar in physicalproperties, e.g., rigidity, elongation at break and hysteresis, to therubber elastomeric materials being bonded and/or repaired.

Protectorants may also be added to the reaction components to provideprotection against environmental hazards. Such protectorants mayinclude, for example, antioxidants, UV absorbers, light stabilizers andcombinations thereof. Reactive polymeric colorants may also be added asreaction components to provide coloration to the polyurethaneureamaterial. For example, if repairing a tire, black colorant may be usedso that the repair material matches the color of the tire. If repairinga white portion of a tire, for example repairing raised white letters onthe tire or white sidewalls on the tire, titanium dioxide may be addedto the repair material to make the repair material white.

Particular embodiments of the polyurethaneurea system may furtherinclude an elastomer-surface activator used to coat the surface of amaterial being bonded or repaired prior to the application of the Part Aand Part B mixtures. The material being bonded and/or repaired by thepolyurethaneurea system of particular embodiments may be an elastomericmaterial and/or a cross-linked rubber material. The use of theelastomer-surface activator provides, in particular embodiments, animproved bonding of the polyurethaneurea formed from the Part A and PartB mixtures to the surfaces being bonded or repaired.

The elastomer-surface activator of particular embodiments may comprise ashort aromatic diisocyanate (as described above) and a prepolymer. Theprepolymer may, for example, be the reaction product between a shortaromatic diisocyanate and a diol as disclosed above. For particularembodiments, the short aromatic diisocyanate of the elastomer-surfaceactivator may be the same as the short aromatic diisocyanate selected asa reaction component of the Part B mixture or the short aromaticdiisocyanate of the elastomer-surface activator may be different thanthe short aromatic diisocyanate selected as a reaction component of thePart B mixture. Particular embodiments include an elastomer-surfaceactivator comprising only the short aromatic diisocyanate and theprepolymer without a solvent while other embodiments include a solvent.

For those embodiments that include a solvent in the elastomer-surfaceactivator, the solvent content is typically between about 35 and about65 wt. % based upon the total mass of the elastomer-surface activator.Suitable solvents include, for example, toluene, ethyl acetate, methylethyl ketone (MEK) or mixtures thereof. Particular embodiments of theelastomer-surface activator comprise an amount of the short aromaticdiisocyanate of between about 0 and about 90 wt. %, or alternativelybetween about 0 and about 80 wt. % or between about 5 and about 80 wt. %based upon the total mass of the diisocyanate in the elastomer-surfaceactivator, the remainder being the prepolymer. Particular embodimentsinclude, for example, an about 50:50 wt. % mix of the short aromaticdiisocyanate to the aromatic diisocyanate prepolymer or alternatively,an about 5:95 wt. % ratio of the short aromatic diisocyanate to thearomatic diisocyanate prepolymer in the activator.

Particular embodiments of the present invention also include methods formaking the polyurethaneurea adhesive/repair material. A particularembodiment includes reacting the Part A mixture with the Part B mixture.In one embodiment, the following amounts (expressed as weight percent ofthe total mass of reactant components) are reacted:

Part A

-   -   a) between about 55 and about 75% of the oligomeric polyol        having an average molecular weight greater than 1000;    -   b) between about 3 and about 7% of an aromatic diamine chain        extender; and    -   c) between 0.1 and 1.5% of the reactivity catalyst.

Part B:

-   -   d) between about 1 and about 15% of the short aromatic        diisocyanate;    -   e) between about 5 and about 35% of the prepolymer.

It may be noted that the rigidity of the polyurethaneurea material maybe adjusted by changing the ratio of the aromatic diamine chain extenderto the polyol in the Part A mixture. By increasing the amount of thearomatic amine, the rigidity typically increases in the resultingpolyurethaneurea material.

Optionally, between about 0 and about 5 wt. % of protectorants and/orcolorants may be added to the reactant mixture. Particular embodimentsmay include between about 0.5 and about 2 wt. % of these materials.Typically these materials may be added to the Part A mixture of reactantcomponents. In particular embodiments, some or all of these componentsmay be added to the Part b mixture of reactant components. It should benoted that if titanium dioxide is used to impart a white color to therepair material, such as for repairing white sidewalls or white raisedlettering on tires, an amount of titanium dioxide greater than thesesuggested amounts is required. Particular embodiments include addingbetween 5 and 18 wt. % of titanium dioxide to the Part A mixture.

Particular embodiments of the method for making the polyurethaneureacomposition include dispensing the two-part reaction mix through anadhesive dispenser and further, through a dispenser that may have astatic mixer. The static mixer, which is typically disposable, ensuresthat the Part A and Part B mixtures are well mixed during the dispensingstep. The adhesive dispenser may be manually, pneumatically orelectrically operated. The adhesive dispenser may be used as analternative to manually proportioning and mixing the Part A and Part Bmixtures.

Such dispensers and their use are well known by those having ordinaryskill in the art and are available, for example, from ConProTec, Inc.,having an office in New Hampshire, under the trade name MIXPAC Systems.The cartridge volume ratio of the adhesive dispenser must be compatiblewith the adhesive formulation. For example, the MIXPAC systems areavailable in models that provide mixed adhesive in mix ratios of the twopart systems of 1:1, 2:1, 4:1 or 10:1.

Bonding and/or repairing elastomer surfaces using particular embodimentsof the polyurethaneurea system may include treating the surfaces to bebonded and/or repaired with the elastomer-surface activator. Inparticular embodiments of the method, at least one of the surfaces to bebonded and/or repaired include an elastomeric surface, some of which mayinclude an elastomer comprising a cross-linked rubber composition.Optionally, but not required, the elastomer surfaces may be cleaned andtreated with a primer to improve the adhesiveness and wetability of thesurfaces to be bonded and/or repaired prior to applying theelastomer-surface activator and/or the polyurethaneurea reactioncomponents. Treatment with such a primer typically removes thecontamination layers or layers of poor adhesion. An exemplary primer is,for example, a solution of trichloroisocyanuric acid (TIC) in a solvent,for example 2-6% TIC in ethyl acetate.

If the primer is used, the primer may be brushed onto the elastomersurfaces and left on the surfaces for about 15 minutes. Then thesurfaces may be rinsed with a solvent, such as with ethyl acetate, toremove any excess TIC. These steps may be repeated until the surface isclean and ready for the elastomer-surface activator and/or thepolyurethaneurea reaction components.

The elastomer-surface activator may be applied to the surfaces to bebonded and/or repaired using a brush, spatula, sprayer or other meansknown to those having ordinary skill in the art. One or more layers ofthe elastomer-surface activator may be applied to obtain the desiredthickness. Particular embodiments include applying a thickness of theelastomer-surface activator of up to about 0.5 mm or alternatively,between about 0.05 and about 0.25 mm. The adhesion of thepolyurethaneurea material is typically improved with the use of theelastomer-surface activator prior to application of the two-partpolyurethaneurea reaction components.

Particular embodiments of repairing an article and/or bonding surfaceswith the polyurethaneurea system may be advantageously carried out atambient temperatures, i.e., between about 20° C. and about 40° C. Ifopposing faces are being bonded together, a pressure of, for example,between about 0.03 bar and about 5 bar, may be applied to the bondingpieces, wherein the duration of exertion is typically proportionatelylonger at lower pressures.

A maturation time for the polyurethaneurea system used in the presentinvention may be used when bonding and/or repairing materials. Thismaturation time may typically be about 48 hours at ambient temperatureor a few hours at a temperature of between 60° C. and 100° C.Advantageously, the polyurethaneurea system formed primarily of primarydiols as discussed above maintains its bonded/repaired state even whensubjected to temperatures of at least 130° C., which is a typical curingtemperature during a tire retreading process using a cushion gummaterial to attach the tread to the tire carcass.

Advantageously, particular embodiments of the polyurethaneurea systemprovides a material that possesses rigidity and hysteresischaracteristics that are quite compatible with the rigidity andhysteresis of various cross-linked rubber elastomers used in tires. Thischaracteristic of the polyurethaneurea material makes it very useful asan adhesive and/or repair material for tires.

Particular embodiments of the present invention include articles havingbonded faces and/or repairs using the polyurethaneurea system disclosedherein. For example, an article according to particular embodiments ofthe invention comprises parts that are bonded together at opposing facesby the disclosed polyurethaneurea system, wherein at least one of theopposing faces comprises a cross-linked rubber composition. After mixingthe polyurethaneurea reaction components, the polyurethaneurea reactioncomponents are typically applied to the opposing faces of the parts, forexample by using a spray gun, a brush or a two-part adhesive gun. Inparticular embodiments, the elastomer-surface activator is applied toboth surfaces of the faces prior to the application of the mixedpolyurethaneurea reaction components.

A particular embodiment of the present invention includes a tire havingan elastomer patch bonded thereto by the polyurethaneurea systemdisclosed herein. The elastomer patch may comprise radio frequencyidentification (RFID) technology and the patch may be bonded to theinner or outer surface of the tire. The patch may include a power source(such as a piezoelectric device or a battery) and/or other electronicssuch as, for example, an antenna, a printed circuit board and atransmitter. Without limiting the invention to specific materials,particular embodiments of the present invention include bonding a patchhaving a bonding surface to an inner liner of a tire. The inner liner ofthe tire is formed of a material that impedes the migration of airtherethrough and typically forms the inner surface of the tire. Inparticular embodiments, the elastomer content of the inner liner of atire includes butyl based rubber as a majority of the elastomericcontent and may typically include between 70 and 100 wt. % butyl basedrubber, between 80 and 90 wt. % butyl based rubber, between 90 and 100wt. % butyl based rubber or 100 wt. % butyl based rubber.

While the patch bonding surface is typically made of a material havingan elastomer content that is diene rubber, particular embodimentsinclude an a bonding surface made of a material having an elastomercontent that is at least a majority of butyl based rubber or between 70and 100 wt. % butyl based rubber, between 80 and 90 wt. % butyl basedrubber, between 90 and 100 wt. % butyl based rubber or 100 wt. % butylbased rubber.

The steps of bonding a patch to a tire include steps such as thefollowing: removing dirt and debris from the bonding area, rougheningthe bonding surfaces of the patch and/or the tire, priming either orboth of the bonding surfaces, applying the surface activator to one orboth of the bonding surfaces, applying the polyurethaneurea adhesivematerial to one or both of the bonding surfaces.

The thickness of the adhesive is typically between about 0.01 mm andabout 2.5 mm. In particular embodiments, the thickness of thepolyurethaneurea adhesive is about 0.6 mm. The patch is then applied tothe surface and pressure is applied until the adhesive is set. Inparticular embodiments, the adhesive may be cured by applying heat tothe patch area. An example of a patch applicator that may be used toinstall a patch with the polyurethaneurea adhesive is disclosed in U.S.patent application Ser. No. 11/967,158 filed 29 Dec. 2007, which ishereby fully incorporated herein.

Other embodiments include bonding articles to a surface of anotherarticle, such as a tire. Such articles that may be bonded to a surfaceof another article such as a tire include, for example, letters made ofan elastomer material or made of metal or fabric. Other articles mayinclude an electronic component or device that may be bonded directly tothe surface of the other article, such as a tire, without mounting orenclosing the electronic component or device in a patch. Non-limitingexamples of such devices may include, for example, an RFID chip, asurface acoustic wave (SAW) sensor, a pressure and/or temperaturesensor. Such devices may be mounted on an inside surface of a tire or onan outside surface of a tire. Such embodiments may include any or all ofthe following steps: cleaning the surface of the article, such as atire; applying (as described above) a primer (such as a solution of TICin a solvent) to the surface; applying (as described above) theelastomer-surface activator to the surface; placing the electroniccomponent or device on the surface of the tire; applying the mixed PartA and Part B reaction components directly over at least a portion of theelectronic component, or device thereby bonding the electronic componentor device directly to the surface. As noted before, in embodiments thatinclude bonding an article to a tire surface, the article (such as anelectronic device or component) may be bonded to the outer or innersurface of the tire.

Optionally, a component such as, for example, an RFID device or a SAWsensor may be applied using a transfer film as known to those havingordinary skill in the art. A transfer film may be a flexible plasticsheet. The device may be placed on the transfer film and then covered atleast partially with the polyurethaneurea components (Part A and Part Bmixtures). The film with the tag may then be placed at the desiredlocation, e.g., the surface of a tire, with the film facing outward. Thefilm may then be peeled off leaving the component bonded to the surface.

A tire or other article comprising an elastomer surface may be repairedby filling a hole, cut, gash, gouge or other opening in the article withthe polyurethaneurea system disclosed herein. Passenger tires, trucktires, motorcycle tires, off-road tires and other types of tires may berepaired or patched using the polyurethaneurea system of the presentinvention. The material is especially useful for repairing a gash, holeor gouge in the sidewall of a tire. In particular embodiments, thearticles are repaired by applying the elastomer surface activator andthen the Part A and Part B mixture.

Particular embodiments of the present invention include repairing thesidewall of very large OTR tires for heavy loads such as those used, forexample, in earth moving tires and mining industry tires. Such tirestypically have a bead seat diameter of at least 25 inches. Sidewallblemishes that occur during the manufacturing process or otherwise canbe repaired in such tires by removing material from the tire to thedepth of the blemish. In particular embodiments, the depth of the repaircan be of any depth as long as the depth does not expose any metal cordsor belts. The surface of the repair area may optionally be buffed toroughen the repair area surface and/or cleaned with a primer.Optionally, the surface may be treated with the surface activator asdisclosed herein. The repair area is then filled with thepolyurethaneurea repair material.

The repair material can then be cured in place without having to placethe tire in a curing chamber for curing at high temperature. Instead,the polyurethaneurea repair material can cure at ambient temperatures,i.e., between, for example, about 15° C. and 50° C. or between about 20°C. and 40° C. In particular embodiments, the curing time is about 48hours but the curing time is dependent on ambient conditions.

Particular embodiments of the present invention therefore include tiresor other articles having elastomeric surfaces to be bonded and/orrepaired with the polyurethaneurea system. In the case of a tire havinga cut, crack, hole or gouge, the area to be repaired is typicallyprepared by removing loose surface material and cleaning the surfacewithin and around the damaged area. Preparation may include buffing thesurface inside the gouge, cut or crack via any conventional apparatus ortreatment.

If cords in the tire have been damaged, the damaged cords may be removedand a reinforced patch applied to the inner surface of the tire as knownto those having ordinary skill in the art. Such cords may be made ofpolyester, nylon, steel, rayon and the like. The reinforced patch may bebonded to the inner surface of the tire using the polyurethaneureasystem disclosed herein. Likewise, if the damage results in a holethrough the sidewall, a patch may similarly be applied to the innersurface of the tire as part of the repair.

The interior faces of the gouge, crack and/or hole may then optionallybe coated with the elastomer-surface activator as described above. Thedamaged area is then filled with the polyurethaneurea material by mixingthe Part A and Part B materials and applying the mixture in the crack orgouge. The material is then allowed to cure at ambient temperature,i.e., between about 20° C. and 40° C. The material can be placed in anautoclave if other repairs to the tire require curing under heat andpressure as known to those having ordinary skill in the art.

Since the curing of the polyurethaneurea material occurs at ambienttemperature, the polyurethaneurea system of the present invention isparticularly useful for in situ repair of large items, such asoff-the-road tires, conveyor belts and the like. The polyurethaneureasystem can be used on the job site with no special autoclaves, steamchambers or vulcanizable tire repair equipment needed.

Particular embodiments of the present invention further include bondinga tread band to a tire carcass, wherein the tire carcass is new or used.Bonding a tread band to a used tire carcass is known as retreading atire. Embodiments of the present invention further include a tire havinga tread bonded thereto with the polyurethaneurea system of the presentinvention.

A retread process of the present invention includes removing the oldtread from a tire carcass, treating the tire carcass with theelastomer-surface activator or treating the tread band with theelastomer-surface activator or treating both with the elastomer-surfaceactivator. The method further includes applying the mixedpolyurethaneurea reactants to the exposed faces of the tread band or thetire carcass or both, and then placing the tread band over the surfaceof the tire carcass.

Particular embodiments of the present invention include bonding orrepairing articles having elastomeric faces, especially those having atleast one face comprising a cross-linked rubber composition. Particularembodiments have at least one face comprising a cross-linked rubbercomposition comprising predominately at least one diene elastomer.

The term “diene elastomer” means an elastomer derived at least in part(i.e., a homopolymer or a copolymer) from diene monomers (monomersbearing two conjugated or unconjugated carbon-carbon double bonds), inparticular:

any homopolymer obtained by polymerization of a conjugated diene monomercontaining from 4 to 12 carbon atoms;

any copolymer obtained by copolymerization of one or more dienes,conjugated together or with one or more vinyl aromatic compoundscontaining from 8 to 20 carbon atoms;

a ternary copolymer obtained by copolymerization of ethylene or of analpha-olefin containing 3 to 6 carbon atoms with an unconjugated dienemonomer containing from 6 to 12 carbon atoms, such as the elastomersobtained from ethylene or from propylene with an unconjugated dienemonomer of the above-mentioned type, in particular, 1,4-hexadiene,ethylidenenorbornene or dicyclopentadiene; or

a copolymer of isobutene and of isoprene (butyl rubber or IIR), and alsothe halogen, in particular chloro or bromo, versions of this type ofcopolymer.

Particularly preferred diene elastomers are chosen from the groupconsisting of polybutadienes (BR), polyisoprenes (IR) or natural rubber(NR), styrene-butadiene copolymers (SBR), terpolymers of ethylene, ofpropylene and of a diene (EPDM), butyl-based rubber and chloroprene.Butyl based rubbers are those that are based on polyisobutylene, whichis a polymerization product of isobutylene and isoprene. Other butylbased rubbers include, for example, halogenated butyl rubbers such aschlorobutyl rubber and bromobutyl rubber.

In a further embodiment of the invention, one of the faces of the partsto be bonded together by the polyurethaneurea system adhesive to obtainthe above-mentioned article comprises a cross-linked rubber composition,while the other face comprises a ferrous metal or an iron-based metalalloy, such as steel.

According to a still further embodiment of the invention, one of thefaces comprises a cross-linked rubber composition, while the other facecomprises a synthetic fabric, such as a fabric of bi-elastic knit typeto form membranes of configuration containing fibers sold under theregistered trademark “LYCRA”.

According to a still further aspect of the invention, one of the facescomprises a cross-linked rubber composition, while the other facecomprises a rigid plastic, such as a thermosetting polyurethane (forexample, application of decoration to tire covers).

The invention is further illustrated by the following examples, whichare to be regarded only as illustrations and not delimitative of theinvention in any way.

Example 1

Batches of the polyurethaneurea systems A1, A2 and A3 were preparedusing the reactant components shown in Table 1. The two-partadhesive/repair materials were prepared by mixing the Part A componentswith the Part B components. These polyurethaneurea materials were thenused to bond two pieces of elastomer together by filling a gap betweenthe two pieces of elastomer with the polyurethaneurea system. Theresulting bonding strengths were then measured.

TABLE 1 Polyurethaneurea Reactant Components Reactant OH NCO AdhesiveMakeup (wt. part) Component Description Index (%) A1 A2 A3 A4 Part AETHACURE 300 aromatic diamine chain 523 6.39 5.53 5.53 5.55 extenderTERATHANE oligomeric polyol 39 91.33 92.16 92.16 92.59 2900 REACTINTpolyol bound colorant 104 0.64 0.65 0.65 0.65 BLACK TINUVIN B75protectorants — 0.73 0.74 0.74 0.74 DABCO 33-LV catalyst 560 0.91 0.920.92 0.46 Part B VIBRATHANE polyether-based aromatic 8.85 13.0 14.451.95 14.4 B836 diisocyanate ISONATE 143L polycarbodiimide-based 29 15.914.4 2.75 14.4 aromatic diisocyanate NCO/(NH₂+OH) molar ratio 1.03 1.031.02 1.03 Surface Activator A2B A3B A3B VIBRATHANE polyether-basedaromatic 8.85 50 95 95 B836 diisocyanate ISONATE 143Lpolycarbodiimide-based 29 50 5 5 aromatic diisocyanate

ETHACURE 300 is a short-chained aromatic diamine chain extenderavailable from Albemarle Corporation. This product is predominately thearomatic diamine 3,5-dimethylthio-2,4- (and 2,6) toluenediamine (DMTDA).TERATHANE 2900 is a oligomeric polyol available from DuPont. Thisproduct is a polytetramethylene ether glycol (PTMEG) having an averagemolecular weight of 2900. REACTINT BLACK X95AB is a polyol boundcolorant available from Milliken Chemical. TINUVIN B75 is a protectorantsystem available from Ciba Specialty Chemicals. ISONATE 143L is apolycarbodiimide-based aromatic diisocyanate available from DowChemical. This modified MDI product is a polycarbodiimide-modifieddiphenylmethane diisocyanate. VIBRATHANE B836 is a polyether-basedaromatic diisocyanate available from Chemtura. This product is anMDI-terminated polyether (PTMEG backbone) diisocyanate. DABCO 33-LV isthe reactivity catalyst triethylenediamine available from Air Products.

The Part A materials were mixed together and the Part B materials weremixed together and each were then loaded into the cartridges of atwo-part adhesive dispenser gun. The cartridges were inserted into thetwo-part cartridge-based adhesive dispenser gun. The ratio that the gundispenser delivered Part A and Part B to the static mixer was 4:1; i.e.,the dispenser delivered 4 times as much volume of Part A as of Part B,for A1 and A2 and 2:1 for A3. The Part A and Part B reaction componentswere mixed by the adhesive dispenser through the attached disposablestatic mixer.

Elastomer-surface activator was also prepared. The elastomer surfaceactivator was prepared by mixing the diisocyanates in the quantitiesshown in Table 1 with a solvent. The weight percent of each of thediisocyanates shown in Table 1 is based upon the total mass of thediisocyanates. The diisocyanates were mixed in a solvent to form theelastomer-surface activator that was made up of 50 wt. % (based on thetotal weight of the solution) of ethyl acetate or toluene as the solventand 50 wt. % of the diisocyanates.

Example 2

Three different rubber elastomer materials were prepared using methodswell known to those have ordinary skill in the art. The three materialswere a sidewall type (SW) rubber composition comprising natural rubberand cis-polybutadiene rubber, an inner liner type (IL) rubber comprisingbutyl rubber and a tread type (T) rubber comprising natural rubber.These materials further comprised vulcanizing agents, etc. as known tothose having ordinary skill in the art.

Each composition was calendered to a thickness of 2.5 mm and cut into15×15 cm squares. These squares were cured in a 15×15 cm mold. A stripapproximately 1.25 cm was cut from each cured square so that each of theremaining parts of the squares were separated by about 1.25 cm. Thevolume between the two parts, which was created by cutting out thestrip, was then filled with the polyurethaneurea material prepared inExample 1. Some of the surfaces were treated with the elastomer-surfaceactivator prepared in Example 1. It should be noted that the Part Acomponents were heated to 40° C. to improve their flow characteristics.After heating to 40° C., the material will cool to room temperature butmaintain good flow characteristics for several hours (4-8) thereafter.

After the polyurethaneurea material filled the gap between the twohalves, the samples were cured in the mold. The mold top exerted apressure of about 1.5 bar on the samples as they were curing. The curingoccurred in the mold utilizing the following procedure: after the topwas set in place, the mold was heated over a 20 minute period to bringthe temperature up from room temperature to 130° C.; the temperature washeld at 130° C. for 100 minutes. After cooling, the squares were removedand each cut into six strips to form 6 samples for testing.

Example 3

The test specimens prepared in Example 2 were tested to determine theirelongation at break property. The elongation property was measured aselongation at break (%), as measured at 23° C. in accordance with ASTMStandard D412 on ASTM C test pieces. Both the elongation at break % andthe break strain (MPa) were recorded. The results are shown in Table 2for test specimens comprising the sidewall rubber (SW) composition, inTable 3 for test specimens comprising the inner liner (IL) compositionand in Table 4 for test specimens comprising the tread (T) composition.

Test specimen No. 1 shown in each of the three tables below was a rubberwitness test. The test results for the rubber witness test provided theelongation at break physical property of the rubber composition itselfwithout being bonded with the polyurethaneurea system of the presentinvention.

As shown in Tables 2, 3 and 4, some of the bonded surfaces of the testspecimens were primed using a solution of trichloroisocyanuric acid(TIC) in a solvent. The tables indicate which of the specimens wereprimed, the solvent used and the number of times the solution wasapplied. For example, test specimen No. 3 shown in Table 2 was primedwith three coatings (brush) of a TIC 5 wt. % in ethyl acetate solution.The sample was allowed to dry for 30 minutes at room temperature afterbeing primed and was washed with ethyl acetate after drying.

Likewise, the tables indicate which test specimens were treated with theelastomer-surface activator comprising the components shown in Table 1of Example 1. The solution of the elastomer-surface activator is alsoprovided in the tables as well as for how long the specimens wereallowed to dry before the PUU formulation was added to the surfaces.

TABLE 2 Test Results for Sidewall Rubber (SW) Composition Test ResultsTIC Primer Surface Activator Break Break PUU Rest Activt'r Rest StressStrain TS Form'n Sol'n (min) Rinse Form'n Sol'n (min) (%) (MPa) 1 NoneNone None 674 20.4 2 A2 None None 0 0 3 [5% EtOAc] × 3 30 yes None 2996.0 4 [5% EtOAc] × 3 30 yes None 303 6.0 5 [5% EtOAc] × 3 30 yes A2B[50% toluene] × 2 30 512 14.5 6 [5% EtOAc] × 3 30 yes A2B [50% EtOAc] ×2 10 522 14.7 7 [5% EtOAc] × 3 30 yes A3B [50% EtOAc] × 2 10 481 13.9 8A3 [5% EtOAc] × 3 30 yes A3B [50% EtOAc] × 2 10 477 13.2 9 A2 [3% EtOAc]× 2 30 yes None 79 1.5 10 [3% EtOAc] × 2 30 yes A2B [50% EtOAc] × 2 10565 16.3 11 [3% EtOAc] × 2 10 yes A2B [50% EtOAc] × 2 10 555 16.9 12 [3%EtOAc] × 2 10 no A2B [50% EtOAc] × 2 10 548 16.4 13 [1% EtOAc] × 2 30yes None 0 0 14 [1% EtOAc] × 2 30 yes A2B [50% EtOAc] × 2 10 383 9.2 15None A2B [50% EtOAc] × 2 10 550 16.2 16 None A2B [50% EtOAc] × 2 10 54516.2 17 None A2B [50% EtOAc] × 1 10 440 11.5 18 None A2B [No solvent] ×1 10 452 11.2

TABLE 3 Test Results for Inner Liner Rubber (IL) Composition TestResults TIC Primer Surface Activator Break Break PUU Rest Activt'r RestStress Strain TS Form'n Sol'n (min) Rinse Form'n Sol'n (min) (%) (MPa) 1None None None 656 13.3 2 A2 None None 251 4.4 3 [5% EtOAc] × 3 30 yesNone 575 11.9 4 [5% EtOAc] × 3 30 yes A2B [50% EtOAc] × 2 10 499 11.3 5[5% EtOAc] × 3 30 yes A3B [50% EtOAc] × 2 10 573 12.4 6 A1 [5% EtOAc] ×3 30 yes A3B [50% EtOAc] × 2 10 534 12.2 7 A2 [3% EtOAc] × 2 30 yes None492 11.0 8 [3% EtOAc] × 2 30 yes A3B [50% EtOAc] × 2 10 586 13.7 9 [3%EtOAc] × 2 10 no A3B [50% EtOAc] × 2 10 617 13.1 10 None A3B [50% EtOAc]× 2 10 599 13.7 11 None A2B [50% EtOAc] × 2 10 533 10.6

TABLE 4 Test Results for Tread Rubber (T) Composition Test Results TICPrimer Surface Activator Break Break PUU Rest Activt'r Rest StressStrain TS Form'n Sol'n (min) Rinse Form'n Sol'n (min) (%) (MPa) 1 NoneNone None 480 22.4 2 A2 None None 0 0 3 [3% EtOAc] × 2 30 yes None 2445.7 4 [3% EtOAc] × 2 30 yes A2B [50% EtOAc] × 2 10 464 19.0 5 A2B [50%EtOAc] × 2 10 507 21.7

The test results shown in Tables 2-5 are plotted in FIG. 4. The selectedzones circles in FIG. 4 define an optimal adhesion condition for each ofthe different rubber compositions.

Example 4

Samples of the A2 material were prepared and allowed to cure intosheets. ASTM C test pieces of each of the rubber compositions (T, SW,IL) that were prepared in Example 2 as well as of the A2 material wereprepared.

The moduli of elongation were then measured on the test pieces at 10%,50%, 100%, 200% and 300% at a temperature of 26° C. in accordance withASTM D412 (1998) on the ASTM C test pieces. These are true secant moduliin MPa, that is to say the secant moduli calculated reduced to the realcross-section of the test piece at the given elongation. Hysteresis wasalso determined on each of the test pieces. The test procedures were runon an INSTRON, Model 5500R test machine.

The results of these tests are shown in FIGS. 1-3. As may be seen fromthese figures, the A2 polyurethaneurea material matches well therigidity and elasticity measurements of the different rubbercompositions. FIGS. 1 and 2 illustrate that the A2 material is morerigid at low deformation. FIG. 3 illustrates the low hysteresis of thematerial at low deformation. Although not clearly shown in FIG. 2, ithas been shown that at high deformation, e.g., above 300% strain, the A2material is softer than the T and SW material.

Example 5

This example illustrates the excellent bonding of a butyl based rubberto a butyl based rubber using the polyurethaneurea adhesive system inaccordance with an embodiment of the present invention. An RFID patchhaving a bromobutyl bonding surface was bonded to a bromobutyl innerliner with the polyurethaneurea adhesive identified as formulation A4 inTable 1 of Example 1. The formulation was prepared as described inExample 1.

The RFID patch was about 4 cm by about 16 cm and was shaped with roundedcorners and with the width of the patch at the center slightly largerthan the widths of the patch at either end. The endurance tests of thepatches mounted to the inner liners the tires were run on two Michelin275/80 R 22.5×DA-HT tires. Each tire had two patches mounted on theinner liner, one patch on the DOT side (A side) and the other patch onthe opposite side (B side). The patches were located about 110 mm fromthe lower lip of the tire.

The patches and the inner liner of the tire were prepared using the TiCprimer and the surface activator as shown in Table 5. The four patchestested are labeled in Table 5 as being on tire 1 and tire 2, either onthe A side (DOT side) or the B side (opposite side). Both the TIC primerand the surface activator were applied with 3 coatings on the patch and5 coatings on the inner liner as described in Table 5.

TABLE 5 Test Results for Butyl Patch Attached to Tire Inner Liner TICPrimer Surface Activator Test PUU Sol'n Rest Activt'r Sol'n Rest ResultsTS Form'n [3% EtOAc] (min) Rinse Form'n [50% EtOAc] (min) Separation 1AA4 3x patch 5x IL 15 yes A3B 3x patch 5x IL 10 None 1B 3x patch 5x IL 15yes A3B 3x patch 5x IL 10 None 2A 3x patch 5x IL 15 yes A3B 3x patch 5xIL 10 None 2B 3x patch 5x IL 15 yes A3B 3x patch 5x IL 10 None

Using the patch applicator described above, the polyurethaneureaformulation was applied to the patch. The thickness of thepolyurethaneurea was 0.6 mm. The patch was applied to the inner linerand a pressure of about 2 bars was applied. The temperature around thepatch was increased from ambient to 127° C. over a 15 minute period andthen the temperature was held at 127° C. for 95 minutes. The patchapplicator was removed and the patch cooled.

The tires were tested on a tire-on-tire test station, i.e., one tirerolling against another tire in a tread-to-tread configuration. Theloading on the tires was 3983 daN with the tire pressure controlled at7.1 bars during the test. The tires were inflated with nitrogen. Thetest was run at 57 km/h with the test cell maintained at 25° C. Thetires were mounted on a 22.5×7.5 wheel.

The testing was run at these conditions for 83, 413 km with periodicstops to examine the patches. During these testing procedures, thepatches remained fully attached to the inner liner of the tires with noseparation anywhere between the patch and the inner liner of the tire.The butyl to butyl bonding by the polyurethaneurea adhesive was robust.

Example 6

This example demonstrates the utility of the polyurethaneurea repairmaterial for repairing raised letters on a tire sidewall. The raisedwhite letters on a tire sidewall were damaged during manufacture,creating a gash in the letter. A form was made having the same height asthe damaged letters. The form was placed against the side of the damagedletter creating a barrier to prevent the repair material from runningout of the repaired area.

The exposed surface of the damaged area was primed with the TIC solutionand then the surface activator A2B (See Table 1) was applied. The A2formulation was prepared as described in Table 1 (except without theblack colorant) and approximately 16 g of titanium oxide was added as awhite colorant.

The repair material was injected into the damaged area and allowed torest for about 2 minutes. Then a spatula was run across the top surfaceto smooth the repair material to the same level as the top surface ofthe letter. The material was then cured at ambient temperature for about48 hours and the form was removed.

The terms “comprising,” “including,” and “having,” as used in the claimsand specification herein, shall be considered as indicating an opengroup that may include other elements not specified. The term“consisting essentially of,” as used in the claims and specificationherein, shall be considered as indicating a partially open group thatmay include other elements not specified, so long as those otherelements do not materially alter the basic and novel characteristics ofthe claimed invention. The terms “a,” “an,” and the singular forms ofwords shall be taken to include the plural form of the same words, suchthat the terms mean that one or more of something is provided. The terms“at least one” and “one or more” are used interchangeably. The term“one” or “single” shall be used to indicate that one and only one ofsomething is intended. Similarly, other specific integer values, such as“two,” are used when a specific number of things is intended. The terms“optionally,” “may,” and similar terms are used to indicate that anitem, condition or step being referred to is an optional (not required)feature of the invention. Ranges that are expressed as being between twopoints, such as between x and y, include x and y in the range.

It should be understood from the foregoing description that variousmodifications and changes may be made in the preferred embodiments ofthe present invention without departing from its true spirit. Theforegoing description is provided for the purpose of illustration onlyand should not be construed in a limiting sense. Only the language ofthe following claims should limit the scope of this invention.

1. A tire for a vehicle, comprising: an inner liner having an elastomercontent that is in majority a butyl based rubber; a patch bonded to theinner liner, the patch having a bonding surface having an elastomercontent that is in majority a diene rubber; a polyurethaneurea adhesivebonding the bonding surface of the patch to the inner liner, thepolyurethaneurea adhesive is the reaction product of reactioncomponents, the reaction components comprising: part A, wherein part Ais a mixture comprising: between about 55 and about 75 wt. % of anoligomeric polyol having an average molecular weight greater than about1000 wherein greater than 75 wt. % of the oligomeric polyols is primaryoligomeric polyol; between about 3 and about 7 wt. % of an aromaticdiamine chain extender; and between about 0.1 and about 1.5 wt. % of areactivity catalyst; and part B, wherein part B is a mixture comprising:between about 1 and about 15 wt. % of a short aromatic diisocyanate; andbetween about 5 and about 35 wt. % of an aromatic diisocyanateprepolymer that is the reaction product of a short aromatic diisocyanateand a diol, wherein the mass fraction of each of the reaction componentsis based upon the total mass of the part A and part B reactioncomponents.
 2. The tire of claim 1, wherein the oligomeric polyolcomprises greater than about 95 wt. % primary oligomeric polyol.
 3. Thetire of claim 1, wherein one or both of the inner liner surface and themounting surface of the patch are treated surfaces, the treated surfacestreated with an elastomer-surface activator comprising a second shortaromatic diisocyanate and a second aromatic diisocyanate prepolymer. 4.The tire of claim 3, wherein at least one of the second diisocyanates ofclaim 3 is the same as at least one of the diisocyanates of claim
 1. 5.The tire of claim 3, wherein the elastomer-surface activator includesbetween 0 and 90 wt. % of the short aromatic diisocyanate, wherein themass fraction is based upon the total mass of the diisocyanates in theelastomer-surface activator.
 6. The tire of claim 5, wherein theelastomer-surface activator includes between 5 and 80 wt. % of the shortaromatic diisocyanate.
 7. The tire of claim 1, wherein the shortaromatic diisocyanate is a polycarbodiimide-modified diphenylmethanediisocyanate.
 8. The tire of claim 1, wherein the short aromaticdiisocyanate is selected from 2, 4 and/or 2,6 toluene diisocyanate(TDI), 4,4′-diphenyl-methane diisocyanate (MDI), polymeric MDI, modifiedMDI compounds, naphthalene diisocyanate (NDI) or combinations thereof.9. The tire of claim 1, wherein the aromatic diisocyanate prepolymer isan MDI-terminated polyether diisocyanate.
 10. The tire of claim 1,wherein the aromatic diisocyanate prepolymer is the reaction product ofthe diol that is selected from a polyether-based diol, a polyester-baseddiol or combinations thereof.
 11. The tire of claim 1, wherein theoligomeric polyol is a polytetramethyleneglycol having an averagemolecular weight between about 1500 and about
 4000. 12. The tire ofclaim 1, wherein the aromatic diamine chain extender is a mixture of 2,4and 2,6 isomers of dimethylthiotoluenediamine.
 13. The tire of claim 1,wherein a ratio of isocyanate functionalities to a total of the amineand hydroxyl functionalities in a mixture of part A and part B isbetween 0.8 and
 2. 14. The tire of claim 13, wherein the ratio ofisocyanate functionalities to the total of the amine and hydroxylfunctionalities in the mixture of part A and part B is between 1.0 and1.07.
 15. The tire of claim 1, wherein the elastomer content of thepatch bonding surface and the inner liner of the tire is between 90 and100 wt. % bromobutyl rubber.
 16. The tire of claim 1, wherein the patchfurther comprises: an electronic component.
 17. The tire of claim 16,wherein the electronic component is a piezoelectric device.
 18. The tireof claim 16, wherein the component comprises an RFID chip.
 19. The tireof claim 16, wherein the article comprises a transmitter and an antenna.